DE1618176A1 - Process for the production of heptenes - Google Patents

Description

Britannic House, Finsbury Circus, London, E.C.2 (England)

Process for the production of heptenes.

The invention has been directed to the preparation of heptenes by a method which is characterized in that a propylene and butene at elevated temperature codlmerisiert over a catalyst obtained by bringing to sodium on an anhydrous potassium compound produced ·

Potassium hydroxide and potassium salts of mineral acids are suitable as potassium compounds. Suitable potassium salts of mineral acids are the silicates, sulfates and halides.

Preferably, molten sodium is vigorously agitated from the potassium compound present in finely divided form. The potassium compound can have the standard of granules, filet, or powder. Usually it is only necessary to carry out the mixing under an inert gas such as nitrogen. The temperature at which the sodium is applied to the potassium compound is not of decisive importance. In general, at temperatures approaching the melting point of sodium, vigorous stirring is required for longer periods than when this is the case

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Sodium is applied at higher temperatures. The temperature is generally selected taking into account any tendency of the potassium compound to decompose, to melt or to sinter. Preferably the conditions and the potassium compound are chosen so that these phenomena do not occur. In general, the sodium metal is applied to the potassium compound at a temperature in the range from 90 to 500 ⁰ O, which is selected accordingly. The amount of sodium used is generally between 1 and 20 wt .- ^ of the potassium compound, preferably between 1 and 7 #

The catalyst, after activation and prior to use preferably with hydrogen at a temperature in the range of 50 to 55O ⁰ O pretreated, as described in British Patent Application 16110/65 the Applicant.

Any butene isomers can be used with propylene in the process according to the invention. Gregebenen trap can also be used as a mixture of two or three isomers. Hydrocarbon fractions which consist of or contain one or more butenes. For example, a butene-containing C, stream from a refinery is suitable.

When the butene isomers are used, the following become On main products received

Insert material product

Propylene and n-butene-3,4-11 B: lmethylpenten-1 and propylene and n-butene-2 J 5-methylhex "n-2 propylene and isobutene _2-t 4-1 Bimethylpenten

They codimerization of propylene and butene is preferably carried out at temperatures ranging from 100 to 200 ⁰ O. Specific preferred temperatures of 120 bie 170 ⁰ O.

109813/1845 ORiGlNAL INSPECTED

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The reaction is usually carried out at normal pressure or elevated pressure, preferably up to 280 atmospheres. The total pressure of the reaction is preferably in the range from 56 to 175 atmospheres, in particular in the range from 98 to HO atü.

The molar ratio of propylene to total butenes is expediently from 1:10 to 10: 1, preferably from 1: 4 to 4j1.

The process can be carried out with or without a solvent will. A sieve is suitable as a solvent. Hydrocarbon e.g. normally liquid paraffins. N-Heptane is particularly suitable.

The feedstock is preferably free of dienes and acetylenes, or at best contains a very low total amount of these compounds. The total content of dienes and acetylenes is preferably below 1.0% by weight, based on the olefinic feedstock.

Examples 1 to 3 6

Dispersions of sodium on potassium carbonate were produced by distributing sodium on anhydrous potassium carbonate ^{at 40O 0 C under nitrogen.} The dispersions in Examples 2 to 6 were ^{treated with hydrogen at 130 °} C. and 70 atmospheres for 20 hours.

The catalysts prepared in this way were used for the dimerization of propylene with η-butene, and isobutene n-butene-isobutene mixtures are used. The reaction conditions and the composition of the starting materials and products are listed in the table below.

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Reaction conditions

Catalyst -. UAA # Na ₂ OO, wt 4.40 3.94 Temperature ■ ^'0 O 170 159 Pressure atm 105 105 total feed, calculated al "Liquid · - V / Y / θ STDL 1.0, £

Hol ratio butene

to propylene 1: 1 2: 1

4.41 4.75 4.46 4.48 160 145 150 150 105 70 70 70

2: 1

2: 1

2: 1

Butene analysis,

Butene-1

Butene-2 (ice + trans)

Isobutene

99.2 0.8

3.4

96.6

2.9
97.1

17.8
30.0
52.2

18.1 29.1 52.8

cc maximum heptene witch //

⁰⁰ Yield, g / hr / mole Na 123 59.0 40 * 41.6 101 29.3 40 25.1 35.7 53 40.9 49 28.3 co witch-heptene analysis, wt. # 4.4 8.1 ^ 4-Me thy lpent e: \ - 1 2.9. • cj 4-methylpentene-2 (cis + trans) 40.5 24.2 ' 16.4. 0.2 " 29.9 20.7 * - Other Cg compounds 13.7 4.4 48.9 9.2 3.5 8.0 4.7 3,4-dimethylpentene-1 4.8 y 41.0 0.2 70.7 48.4 64.3 3 '°. 59.1 2 ,? 71.1 3,4-dimethylpentene-2 (ice + tzaoe) 18.4 " 0.4 0 Γ 7.1 11.7 ^- 15.0 2,4-dimethylpentene-1 2.8 19.9 3 ^ 7 0.1 3l6 4.3 2,4-dimethylpentene-2 (cie + trans) 0.1 51.2 2.5 27.8 35.3 5-ethylhexene-2/4-ethylhexene-1 0.4 2.0 51.1 9.5 2l5
m 2.2 2.2 4,4-dimethylpentene-1 14.7 0.2 4l6 5.4 Other C ^ compounds 0.1 2.4 3.1 2.7 4.5 3.6
al * '\ 6.8

Claims (1)

1) Process for the preparation of heptenes, characterized in that propylene and a butene Del increased Temperature codimerized over a catalyst which has been prepared by applying sodium to an anhydrous potassium compound. 2) Method according to claim 1, characterized in that the catalyst is activated by pretreatment at elevated temperatures before it is used in the codimerization. 5) Method according to claim 2, characterized in that activation takes place at temperatures above the melting temperature of sodium. 4) Method according to claim 2, characterized in that the activation treatment of the catalyst at temperatures in the range of 5 < Hydrogen takes place. temperatures in the range from 50 to 35O ⁰ C in the presence of 5) Method according to claim 1 to 4, characterized in that that 4a «as a potassium compound potassium hydroxide or a Potassium salt of a mineral acid, such as potassium sulfate, silicate or halide, but in particular potassium carbonate, is used, the potassium compound in the form of granules, Pellets or powder can be used. 6) Process according to claim 1 to k, characterized in that catalysts are used in which the sodium has been applied to the potassium compound in the temperature range from 90 to 500 ^° C. 7) Method according to claim 1 to 6, characterized in that that it is carried out with catalysts, the sodium in an amount between 1 and 20 Oew.-Ji of the potassium compound 109813/1845 hold, preferably using catalysts with a sodium content between 1 and 7 Qew .- #. 8) Method according to claim 1 to 7 »characterized in that that a mixture of 2 or 3 butene isomers is used, one also using a butene-containing C ^ refining stream can work. 9) Method according to claim 1 to 8, characterized. that the codimerization at temperatures in the range from 100 to 200 ⁰ C, before: is carried out. 100 to 200 ^° C., preferably in the range from 120 to 170 ^° C. 10) Method according to claim 1 to 9 * characterized in that that the codimerization is carried out at pressures from 56 to 175 kg / cm, preferably in the range from 98 to 140 kg / cm will. 11) Method according to claim 1 to 10, characterized in that that the ratio of propylene to Oesamtbutenen im Range from 1:10 to 10: 1, preferably within the Range from 1: 4 to 4: 1. 12) Method according to claim 1 to 11, characterized in that that the process in the presence of a solvent, e.g. B. is carried out in the presence of n-heptane. 13) Method according to claim 1 to 12, characterized in that "on" in outputs "material starts that is free of Serving and acetylene compounds is 109813/1845